有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
総説および総合論文
電子豊富な二核ルテニウム錯体を触媒としたピリジンおよび環状アミンの変換反応
高尾 俊郎
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2020 年 78 巻 4 号 p. 327-337

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The reactivity of transition metal clusters has been of special interest in these days in the area of organometallic chemistry, owing to their capability of activating substrates through the cooperative effects of multiple metal centers. Although the multiple coordination to the metal centers enables facile bond activation of the substrates, the formed multiple M-C bond are an obstacle to the elimination of the substrates from the multinuclear site. However, we found that electrostatic repulsion of the substrate with the electron-rich multinuclear site comprised of (C5Me5)Ru fragments and stabilization by the recovery of aromaticity could be a driving force for the elimination from the multinuclear site. Thus, we attempted the reaction of polyhydrido clusters with pyridines to design a novel cluster catalysis. We report herein dehydrogenative coupling of 4-picoline and dehydrogenative oxidation of cyclic amines catalyzed by diruthenium complexes, [(CpsRu)(µ-H)2]2 (Cps=C5Me5 and C5tBu3H2), which involve unique chemical transformations at a diruthenium site.

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